US5714244A - Method for protecting a porous carbon-containing material from oxidation, and material obtained thereby - Google Patents
Method for protecting a porous carbon-containing material from oxidation, and material obtained thereby Download PDFInfo
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- US5714244A US5714244A US08/564,133 US56413395A US5714244A US 5714244 A US5714244 A US 5714244A US 56413395 A US56413395 A US 56413395A US 5714244 A US5714244 A US 5714244A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/16—Two dimensionally sectional layer
- Y10T428/161—Two dimensionally sectional layer with frame, casing, or perimeter structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/16—Two dimensionally sectional layer
- Y10T428/162—Transparent or translucent layer or section
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249956—Void-containing component is inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249956—Void-containing component is inorganic
- Y10T428/249957—Inorganic impregnant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention concerns the protection of porous carbon-containing materials against oxidation and catalytic oxidation of the carbon.
- the field of the invention is that of carbon-containing porous materials for use at temperatures above the temperature at which oxidation of carbon commences, i.e., about 350° C., up to about 1000° C.
- These materials are solid materials such as porous graphites and carbons, and also composite carbon-containing materials.
- these latter materials are composite materials constituted by reinforcing fibers densified by a matrix, carbon being present in the fibers, in the matrix and/or in a matching or interphase layer between the fibers and the matrix.
- composite materials of this type are thermostructural composite materials in which the reinforcing fibers and the matrix are formed from carbon or a ceramic with the possible interposition of a pyrolytic carbon interphase between the fibers and the matrix. These materials are characterized by their good mechanical properties. When they contain carbon, retaining these properties at high temperature in an oxidizing environment requires the presence of effective protection against oxidation.
- thermostructural composite materials --densification from a liquid consisting of impregnating the reinforcing fibers with a precursor and then transforming the precursor by heat treatment, or densification by chemical vapor infiltration--the materials obtained have a residual open pore space, giving oxygen from the surroundings access to the core of the material.
- a first aim of the invention is to provide effective protection against oxidation to solid or composite carbon-containing materials with an internal pore space which is accessible from the outside.
- a further aim of the invention is to provide effective protection against catalytic oxidation of carbon.
- the reaction between carbon and oxygen is known to be accelerated by the presence of certain elements, such as alkalis and alkaline-earths, which are introduced by or provided by, for example, sodium chloride (sea water), potassium acetate, etc., which act as oxidation catalysts.
- These catalysts may be impurities from the surroundings (pollution, soiling, exposure to a marine environment, etc.) or impurities from a manufacturing process, for example residues from the manufacture of carbon fibers (precursors, sizing substances added prior to weaving).
- a well-known process for protecting a carbon-containing material against oxidation consists of forming a coating which constitutes a barrier against oxygen from its surroundings.
- a coating which constitutes a barrier against oxygen from its surroundings.
- self-healing oxidation protection or protection which is completed by an additional covering layer with such a property, is also used.
- self-healing here means the ability to fill in automatically any crack of fault which may appear during use of the material.
- Coatings in the form of glasses are used to constitute self-healing protection for materials for use at relatively high temperatures. By becoming viscous at the working temperature of the material to be protected, glasses are able to fill in any cracks. The composition of the glass is selected so that it has the desired viscous character at the intended working temperature.
- glasses with a low melting point are suitable, i.e., glasses with a glass transition temperature T g of not greater than 500° C.
- T g glass transition temperature
- effective oxidation protection is required from the temperature at which oxidation of carbon commences, it may be relatively low, from 250° C. to 350° C. It may be slightly higher, for example about 450° C. to 500° C., depending on the working temperature range of the material, and providing an absence of a self-healing function between 350° C. and 450° C. to 500° C. is tolerable since the oxidation kinetics of carbon are still fairly slow.
- the effective range of the glass i.e., the range in which self-healing is effective, is about 500° C.
- a value of T g of 250° C. to 350° C. can provide protection up to about 750° C. to 850° C.
- a value of T g of 450° C. to 500° C. provides protection up to about 950° C. to 1000° C.
- glasses with low melting points which appear to be particularly suitable are phosphate based glasses, i.e., glasses in which the principal glass forming oxide is P 2 O 5 .
- phosphates, whether glasses or not also have anti-catalytic activity as regards the catalytic oxidation of carbon.
- phosphates can inhibit the effect of catalytic agents present in contact with a material to be protected, thereby returning the oxidation kinetics to that of pure carbon.
- phosphate based glasses can both counter the action of the catalyst and act as a self-healing barrier.
- U.S. Pat. No. 3,351,477 describes the use of an impregnating composition constituted by a relatively concentrated aqueous solution, and stipulates a particular order of introducing the precursors for the phosphate coating to be produced.
- dissolution of the precursors begins with phosphoric acid whose presence allows the other precursors to dissolve, but to a limited degree. This results in the formation of a phosphate coating which is sensitive to moisture.
- the phosphoric acid has a tendency to volatilize, making it difficult to fix the final composition and thus to fix the properties of the phosphate coating produced.
- FR-A-2 685 694 describes impregnating a composite material with a liquid solution of sodium and potassium phosphates, before drying and heat treatment to form an internal protective layer against oxidation which covers the surfaces of the open pores in the material. The protection obtained is again too sensitive to moisture.
- a known solution described by L. Montague et al. in "Journal of Non-crystalline Solids", 155, (1993), April, No 2, Amsterdam, NL, pp. 115-121, consists of incorporating a modifying oxide precursor, in this case alumina, into a polyphosphate solution to obtain a gel, from which a phosphate based glass with an increased resistance to moisture corrosion can be produced.
- a modifying oxide precursor in this case alumina
- Another known solution also consists of adding modifying oxides, in particular zinc oxide ZnO, and producing the glass by melting a mixture of its different constituents.
- Impregnation of the porous material to be protected with a melted glass-containing base can also be envisaged. However, this raises problems. Firstly, it would be necessary to operate under pressure and at a high temperature, which would render the process complex and costly. Secondly, the pores in the materials, whether carbon or solid graphite or a densified composite material, are small, so deep impregnation requires an impregnating composition with low viscosity, less than that of molten glass.
- a further possibility could consist of introducing the constituents of the modified phosphate type glass-containing base, or its precursors, in the form of powders suspended in a liquid vehicle, impregnating the porous material with this suspension, then forming the glass-containing base by heat treatment, after drying the impregnated material.
- the pores have dimensions which are too small to allow deep infiltration by the solid particles.
- the most suitable technique thus appears to be impregnation of the porous material by a completely dissolved aqueous solution of precursors of the desired phosphate type glass-containing base.
- the aim of the present invention is to provide a process which can form an internal oxidation protection in the form of a phosphate type glass-containing base which is highly insensitive to moisture in a porous carbon-containing material, by impregnating the material with an aqueous solution of precursors for the glass-containing base.
- a further aim is to carry out the impregnation with an aqueous solution in which the concentration of precursors is as high as possible to obtain a high degree of impregnation and produce the desired internal protection in a single impregnation step.
- the precursors are introduced into the aqueous solution so as to allow the formation of a glass-containing base in which the molar ratio between the glass modifying oxides, comprising zinc oxide, and the glass forming oxides, principally comprising or consisting of phosphoric anhydride, is sufficiently high to confer a resistance to corrosion by moisture on the glass-containing phosphate base, and
- the solution is formed by firstly dissolving in water, a polyphosphate which can then allow the required quantity of precursor salts of the modifying oxides comprising at least one zinc salt to dissolve to form a stable solution without the formation of a precipitate.
- glass-containing phosphate base here means both a phosphate based glass and a phosphate based composition which, on melting, behaves as a glass but in which a crystalline phase may appear on cooling and/or with time, leading to partial devitrification (a glass containing crystal grains).
- the molar ratio between the modifying oxides and the glass forming oxides which must be achieved to obtain high resistance to corrosion by moisture depends on the nature of the constituents of the glass-containing base, in particular the modifying oxides present with the zinc oxide.
- the molar ratio between the ZnO and the P 2 O 5 is preferably greater than one.
- the corrosion rate is divided by a factor of about 100 when the molar ratio between ZnO and P 2 O 5 passes from a value slightly below one to a value slightly greater than one.
- the minimum value of the molar ratio between the modifying oxides and the forming oxides can be less than one. It appears, however, to be preferable that this ratio is at least 0.6 at all times, and better still at least 0.9.
- the phosphate which is dissolved first is a polyphosphate, advantageously sodium metaphosphate or sodium trimetaphosphate, which allows the required proportion of precursors to dissolve by complexing the cations which are subsequently produced.
- the precursor salt for zinc oxide preferably zinc nitrate or zinc sulfate, is introduced next into the solution.
- the viscosity of the solution must, however, be sufficiently low to allow deep impregnation into the material, in particular when the accessible open pore space has small dimensions, as is the case for solid carbons and graphites or carbon-containing composites.
- the viscosity is typically in the range 0.1 dPa.s to 10 dPa.s, preferably in the range 0.1 dPa.s to 1 dPa.s.
- the stability of the solution can be improved still further while keeping the acidity fairly high, preferably at a pH of less than 0.5.
- This acidity is achieved by adding suitable oxide precursors, for example potassium dihydrogen phosphate, boric acid, ammonium phosphate etc., but excluding phosphoric acid.
- one or more organic stabilizing agents with a fugitive nature can be added to the precursors, i.e., totally eliminated during the final heat treatment.
- these fugitive stabilizing agents are oxalic acid, tartaric acid and citric acid.
- oxide precursors such as: copper, cobalt, nickel, iron, magnesium and/or lead oxides, lithium and/or potassium oxide precursors, bismuth, aluminium and/or boron oxide precursors and vanadium and/or titanium oxide precursors.
- a precursor of this oxide for example ammonium phosphate, but excluding phosphoric acid, can be added to the solution.
- a further object of the invention is provided by a porous carbon-containing material provided with an internal oxidation protection and catalytic oxidation of carbon, the internal protection being constituted by a layer fixed in the pore space of the material and formed by a glass-containing phosphate base modified at least by the presence of zinc oxide, in which material, in accordance with the invention, the glass-containing base has the following composition, in moles of oxides:
- At least one oxide selected from V 2 O 5 and TiO 2 with a molar ratio between the modifying oxides, comprising zinc oxide, and the forming oxides, principally comprising or consisting of phosphoric anhydride, which is sufficiently high to confer a resistance to corrosion by moisture on the glass-containing phosphate base.
- the invention is remarkable in that the deposit is fixed in the core of the accessible pore space of the porous material to be protected, to constitute an internal protection covering the surfaces of the open pores.
- composition defined above in addition to phosphoric anhydride P 2 O 5 which constitutes the principal or unique glass forming oxide, other oxides which are normally formers which may be present are boron oxide B 2 O 3 and vanadium oxide V 2 O 5 , the other oxides being the modifying oxides.
- the nature and respective quantities of the constituents of the solution used to impregnate the material to be protected are selected depending on the desired composition of the glass-containing base and the possibility of introducing these constituents in the required quantities into a stable aqueous solution.
- modifying oxides in large proportions in the glass-containing base is indispensable in order to produce the desired moisture resistance.
- a polyphosphate such as sodium metaphosphate NaPO 3 or sodium trimetaphosphate is employed.
- P 2 O 5 may also be provided by the presence of other phosphates such as ammonium phosphate NH 4 H 2 PO 4 or potassium phosphate KH 2 PO 4 , the latter also being capable of maintaining the desired acidity for the stability of the solution.
- other phosphates such as ammonium phosphate NH 4 H 2 PO 4 or potassium phosphate KH 2 PO 4 , the latter also being capable of maintaining the desired acidity for the stability of the solution.
- the precursor of B 2 O 3 is, for example, boric acid H 3 BO 3 , and that of V 2 O 3 may be ammonium vanadate NH 4 VO 3 .
- the precursors for the metallic oxides, in particular ZnO, and the alkali metal oxides are, for example, nitrates or sulfates.
- the ZnO precursor is zinc nitrate Zn(NO 3 ) 2 ,6H 2 O.
- the combination of sodium metaphosphate and zinc nitrate has the particular characteristic of forming a complex which then prevents the Zn 2+ cation which would be produced if a different method were used, from precipitating long chains of sodium phosphate.
- the aqueous solution of glass-containing base precursors is produced by firstly introducing into water, a condensed phosphate, in these examples sodium metaphosphate, then secondly a ZnO precursor salt, in these examples Zn(NO 3 ) 2 ,6H 2 O, the subsequent order of introduction of the remaining precursors being less critical.
- Impregnation of the material to be protected is, for example, carried out at room temperature by immersing the material in a bath of the aqueous solution of precursors which has a viscosity in the range 0.1 dPa.s to 10 dPa.s.
- a vacuum is established before or after immersion, or an overpressure is established after immersion, in order to allow the solution to infiltrate the accessible pore space of the material.
- heat treatment is carried out so that the glass-containing base composition can reach its physico-chemical equilibrium.
- heat treatment is carried out at a temperature of about 350° C. to 950° C.
- Heat treatment is preferably carried out in a neutral atmosphere, for example in nitrogen (N 2 ). It can also be carried out in a reactive atmosphere, for example a nitriding atmosphere, in ammonia which may contain additional hydrogen (NH 3 +H 2 ); nitriding of the glass-containing base may further increase its resistance to corrosion by moisture.
- a neutral atmosphere for example in nitrogen (N 2 ). It can also be carried out in a reactive atmosphere, for example a nitriding atmosphere, in ammonia which may contain additional hydrogen (NH 3 +H 2 ); nitriding of the glass-containing base may further increase its resistance to corrosion by moisture.
- This example compares the resistance to moisture of a glass (glass 1) with a composition which is that of a prior art internal protective coating against oxidation, more precisely that described in French patent FR-A-2 685 694 described above, with the moisture resistance of glasses (glasses 2 and 3) with compositions which are those of an internal protective coating against oxidation formed in accordance with the invention.
- Table 1 shows the compositions of the solutions produced to obtain glasses 1, 2 and 3, also the order of introduction of the precursors for glasses 2 and 3.
- the precursors were dissolved in 30 cm 3 of water.
- the concentrations of the precursor solutions are also shown, along with the glass yield of each solution.
- the paste recovered from each solution was gradually raised to a temperature of about 900° C. for one hour in a refractory crucible in a neutral atmosphere, during which phase the precursors were transformed into a glass.
- Glasses 1, 2 and 3 obtained were poured into solid rods with a mass of about 3 grams (g), into a solid carbon mould.
- Table II shows the composition, in molar percentages of oxides, of glasses 1, 2, and 3, and their transition temperature T g .
- the glass rods were each immersed in 100 ml of water at 100° C. Glass rod 1 had completely dissolved after 10 minutes. Glass rods 2 and 3 were left for one hour and the weight loss was measured. Table II indicates the corrosion rates for the glasses as a percentage loss per minute.
- forming a glass with a process according to the invention allows a quite significant increase in the resistance to corrosion by moisture, while retaining the use of a stable and concentrated aqueous solution with high efficiency and low melting point.
- This example shows the effectiveness of an internal protection obtained in accordance with the invention against oxidation and catalytic oxidation of carbon.
- the samples were then oven dried and heat treated in a neutral atmosphere at a temperature of about 750° C.
- composition obtained had the following molar percentages of oxides:
- the relative weight of glass in the samples was about 2%.
- This example shows the homogeneity of the oxidation protection in the volume of the treated piece.
- Parallelepipedal samples with dimensions of 25'20'6 mm 3 were taken from the center of the cylinder and impregnated with a solution of a carbon oxidation catalyst (in this case potassium acetate). The treated samples were then kept in air at 650° C. for 5 hours. The average relative weight loss was 0.7%.
- This example shows the possibility of adjusting the composition of the glass to improve one of its properties or provide it with a particular property, by addition of a suitable precursor.
- the wetting power of the glass on a carbon surface was to be improved in order to complete its protective function. This was achieved by adding vanadium oxide V 2 O 5 to the glass composition.
- aqueous solution was used with the following composition in weight percent (the figure in parentheses indicates the order of introduction of the precursors into the solution):
- composition obtained (glass 5) had the following molar percentages of oxides:
- aqueous solution was prepared with the following composition by weight (the figure in parentheses indicates the order of introduction of the precursors into the solution):
- composition obtained (glass 6) had the following molar percentages of oxides:
- Example 1 the glass was moulded into a solid rod and kept for one hour in 100 ml of water at 100° C.
- this example sought to increase the resistance to corrosion by water, while maintaining a high level of oxidation protection.
- Example 2 Carbon-carbon samples identical to those described in Example 2 were provided with an internal protection constituted by glasses 4 (Example 2) and 7 (samples I and II respectively) following the process described in Example 2.
- the treated samples were kept in water at room temperature for 16 hours.
- the corrosion rates for the glasses measured as a percentage of the weight loss, were:
- alumina substantially increased the resistance to corrosion by water.
- This does not exclude the possibility of combining this internal protection with an external oxidation protection in the form of a surface coating fixed in the superficial pore space of the material.
- This external protection is effected, for example, by spraying or painting a composition in the form of a solution or suspension of external protection precursors which, after drying, undergo heat treatment.
- the composition containing the precursors for the external protection can be used after impregnation with the internal protection precursor composition and any required drying, the internal and external protections then being generated by the same heat treatment step.
- an analogous composition to the internal protection precursor impregnating composition for the external protection precursor composition is advantageous to use.
- a variety of constituents can be added, in suspension or in solution, to provide the external protection with specific properties.
- refractory oxides for example colloidal silica (SiO 2 )
- SiO 2 colloidal silica
Abstract
Description
TABLE I __________________________________________________________________________ Glass Glass Glass solution 1 solution 2 solution 3 Composi- Composi- Order of Composi- Order of tion of pre- tion of pre- introduction tion of pre- introduction Precursors cursors (g) cursors (g) of precursors cursors (g) of precursors __________________________________________________________________________ NaH.sub.2 PO.sub.4 22.5 NaPO.sub.3 12.2 1 6.8 1 Zn(NO.sub.3).sub.2, 15.8 2 13.4 2 6H.sub.2 O 2.3 3 LiNO.sub.3 7.5 5.5 3 4.6 4 KH.sub.2 PO.sub.4 11.6 5 NH.sub.4 H.sub.2 PO.sub.4 1 6 H.sub.3 BO.sub.3 Concentration of 1000 1000 1000 precursors (g/l) Glass yield (g/l) 850 600 650 __________________________________________________________________________
TABLE II ______________________________________ Constitution in molar % of oxides Glass 1 Glass 2 Glass 3 ______________________________________ P.sub.2 O.sub.5 50 37.4 46.5 ZnO 25.2 20.4 Na.sub.2 O 38.6 28 5.1 K.sub.2 O 11.4 9.3 7.6 Li.sub.2 O 7.6 B.sub.2 O.sub.3 3.8 T.sub.g (°C.) 270 270 270 Corrosion rate 10 0.2 0.1 (% wt/min) ______________________________________
______________________________________ H.sub.2 O 42.5% NaPO.sub.3 (1) 16.6% Zn(NO.sub.3).sub.2,6H.sub.2 O(2) 20.7% KH.sub.2 PO.sub.4 (3) 6.5% H.sub.3 BO.sub.3 (4) 1.6% H.sub.6 NPO.sub.4 (5) 12.1% ______________________________________
______________________________________ P.sub.2 O.sub.5 45.6% ZnO 20.2% Na.sub.2 O 23.5% K.sub.2 O 6.9% B.sub.2 O.sub.3 3.8% ______________________________________
______________________________________ samples A 0.1% samples B 0.3% samples C 5% samples D 99% ______________________________________
______________________________________ H.sub.2 O 42.7% NaPO.sub.3 (1) 16.1% Zn(NO.sub.3).sub.2,6H.sub.2 O(2) 20.1% KH.sub.2 PO.sub.4 (3) 6.3% H.sub.3 BO.sub.3 (4) 1.6% NH.sub.4 H.sub.2 PO.sub.4 (5) 11.7% NH.sub.4 VO.sub.3 (6) 1.5% ______________________________________
______________________________________ P.sub.2 O.sub.5 44.8% ZnO 19.8% Na.sub.2 O 23% K.sub.2 O 6.8% B.sub.2 O.sub.3 3.7% V.sub.2 O.sub.5 1.9% ______________________________________
______________________________________ H.sub.2 O 30 g NaPO.sub.3 (1) 12.2 g Zn(NO.sub.3).sub.2,6H.sub.2 O(2) 15.8 g KH.sub.2 PO.sub.4 (3) 5.5 g CuSO.sub.4,3H.sub.2 O(4) 12.2 g ______________________________________
______________________________________ P.sub.2 O.sub.5 30.4% ZnO 20% CuO 19.2% Na.sub.2 O 22.8% K.sub.2 O 7.6% ______________________________________
______________________________________ P.sub.2 O.sub.5 46.3% ZnO 16.2% Na.sub.2 O 20.3% K.sub.2 O 5.9% B.sub.2 O.sub.3 3.3% Al.sub.2 O.sub.3 7% ______________________________________
______________________________________ for samples I (glass 4) 1.87%/hour for samples II (glass 7) 0.03%/hour. ______________________________________
______________________________________ for samples I (glass 4) 0.38% for samples II (glass 7) 0.31%. ______________________________________
Claims (29)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9403971 | 1994-04-05 | ||
FR9403971A FR2718129B1 (en) | 1994-04-05 | 1994-04-05 | Process for the protection against oxidation of a porous material containing carbon, and material obtained. |
PCT/FR1995/000432 WO1995026934A1 (en) | 1994-04-05 | 1995-04-05 | Method for protecting a porous carbon-containing material from oxidation and material obtained thereby |
Publications (1)
Publication Number | Publication Date |
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US5714244A true US5714244A (en) | 1998-02-03 |
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US08/564,133 Expired - Lifetime US5714244A (en) | 1994-04-05 | 1995-04-05 | Method for protecting a porous carbon-containing material from oxidation, and material obtained thereby |
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US (1) | US5714244A (en) |
EP (1) | EP0701538B1 (en) |
JP (1) | JP3535874B2 (en) |
CA (1) | CA2164092C (en) |
DE (1) | DE69510626T2 (en) |
ES (1) | ES2135726T3 (en) |
FR (1) | FR2718129B1 (en) |
RU (1) | RU2136636C1 (en) |
UA (1) | UA43845C2 (en) |
WO (1) | WO1995026934A1 (en) |
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US7641941B2 (en) | 2003-04-22 | 2010-01-05 | Goodrich Corporation | Oxidation inhibition of carbon-carbon composites |
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US20070099787A1 (en) * | 2005-04-22 | 2007-05-03 | Joseph Hayden | Aluminophosphate glass containing copper (II) oxide and uses thereof for light filtering |
US20070154712A1 (en) * | 2005-12-22 | 2007-07-05 | Mazany Anthony M | Oxidation inhibition of carbon-carbon composites |
US20100266770A1 (en) * | 2005-12-22 | 2010-10-21 | Goodrich Corporation | Oxidation inhibition of carbon-carbon composites |
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US10703669B2 (en) | 2017-04-28 | 2020-07-07 | Schott Ag | Filter gas |
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Also Published As
Publication number | Publication date |
---|---|
UA43845C2 (en) | 2002-01-15 |
EP0701538B1 (en) | 1999-07-07 |
CA2164092C (en) | 2004-07-13 |
RU2136636C1 (en) | 1999-09-10 |
JP3535874B2 (en) | 2004-06-07 |
ES2135726T3 (en) | 1999-11-01 |
JPH08511232A (en) | 1996-11-26 |
FR2718129B1 (en) | 1996-06-21 |
FR2718129A1 (en) | 1995-10-06 |
DE69510626T2 (en) | 2000-03-02 |
CA2164092A1 (en) | 1995-10-12 |
DE69510626D1 (en) | 1999-08-12 |
EP0701538A1 (en) | 1996-03-20 |
MX9505038A (en) | 1998-03-31 |
WO1995026934A1 (en) | 1995-10-12 |
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